Process for purifying crude benzene



April 25, 1961 E. sATTLr-:R- 2,981,766

PROCESS FOR PURIFYING CRUDE BENZENE Filed April 22, 1957 Unite 2,981,766 :tRCASS FOR PURIFYING `CRUDE` BENZENE Sattler, IEssen, iGer'nimpl'y, assignor, "by mesne assignments, to Kappers Company, Inc., Pittsburgh, -Pa.,

fa'corporation of Delaware States Y Pater-rt 12,910,517, dated October `27, 1959,-led`December 5, i

T1956 by this inventor Sattler and Willi Oettinger, `and `referred to hereinafter, of pressure-refining `of vcrude ebenzene, when the fresh hydrogen-gas, which is con- .-stantlyl supplied for replacing `thehydrogen consumed during the refining operation, consists of coke-oven `gas -or--towngas, special measures are necessary in orderk to Aprevent an undesirable consumption -oflhydrogen from --takingplace due to the carbon monoxide contained-.in ithet'fresh gas beingpartiallyconverted with-the hydrogen into methane. Consequently, it'has been proposed Yin my aforesaid joint invention Patent No.2;91i0,5l7,.based ,1 oni application -Serial No. 626,424iiled DecemberyS, 1956 `that the fresh -gas that is to be introducedl into `the procf-ess as replacement for the-hydrogen consumed should be-introduced into the catalytic treatment stage '(reactor) `in such-manner that it initially enters a zone ofthe `reactor where an increased -carbonA monoxideandtsteam -coneentration nis present, in `Awhich zone r the `carbon ymonoxide of the 'fresh gas containing? carboni-'monoxide `f1andfsaturated -with'- steam` ,which-` hast been-heated` in' the if cylinder 'byheat absorption `from f-the recycle gas i s-` pref- @crentially -convertediinto hydrogen andr carbon dioxide rather than methane. It is` only thenthat .-the fresh;` gas `treatedinhis manneris tor-be` v'combined with-thererHmainder of -therecycle-gas. =Withtthe .conversion of the :carbon: monoxide contentof the fresh-@gas within, the

especial initial zone ofthe reactor,fthereis simultaneously Vobtaineda reduction-of :the sulphurous:-andnnitrogenous ,-:compounds-,of-` the 'fresht` gas; Moreiespecially, the `nitric that cokei-ovenf'gas, becauseittcontains nitricoxideas well as hydrogen sulphide, cannottreadily be brought-to the reactor working pressureiofabout 40-750 atm. Aiactully, if the pressure ofagas containing hydrogen sulphide and nitric `oxide exceeds the .value of `about-5.15 atm.` atthe mostresnous bodies-are`formedby arcaction between thefhydrogensulphide and the nitric oxide,

rthesebodies clogging the compressorr and connected pressure pipes and equipment. According toan `invention vofftheapplieants whichhas not yet been published,``this Idilcultycan be avoided ifthecoke-oven` gas ,is Icompressed in a multi-stage compressor initially only to a l,pressure of `l5V atm. Aatfa` maximum'. and Athe :gas ist ,then

largelydesulphurised under pressure and thereafter; Vthe desulphurised gast-is brought-'in the followingstageaof the Y.compressor to Athe necessary working pressure for the .refining` operation. '.Thus lwhile it-'has in fact been .show-n. that iflhydrogenfsulphide is removed to afsutl'icient `degree atf15.atm.,."the residual-nitric oxides do -nottshow -any tendency-to formtresinous bodies, eventat .greatly increased c pressure '.with this invention, which `-has -not -yet been published, lit,isjneverthelessfnecessary: to have la separate device `for t extracting 4the -sulphur from -thef gas brought` to =a predetermined gtpartialpressure.

lThe present inventionA obviates this. separate sulphurypurification plant,V in that. itgsoqmodies the arrangement of .the main: inventionl that` this` arrangement can` also be used for aA fresh 4@gas from whichf sulphur f liasnot-pre- -tviouslyv-been removed ,before thetagas is-` raised--to-Work- A:ing-,pressure for-'the-lrefining operation.

The present improvement' resides Ain continuing the `invention of the aforesaid cylinder Withinthe reactor t but ina-a` form which `is operable.` under-fa lower pressure thefreshgas to the cylinderchamberr` atta-,pressure which .is belowl'the ,workings pressure ofthe@` reactor, preferably ata-pressure of l0-',l5 atm., `andfthereafter bringingfcthe freshgas -to the-maximunnworking. pressure-for ,-the reacttor; andeonly then'` combining the fresh-gas t with thefrecycle-,gas before yor avi-th theftpassage :thereofA1 through:` the fromtheworkingapressure in the-reactor and supplying Y reaction chamber.

t. oxidecontained `in the l 'fresh -gasgis: reduced t :to @nitrogen y r the reactor. and 4separated therefrom, which-chamber assqufntlyfbeins .subjected mandaat-heat @Xhangenrith i the hot recycle gas externally of the cylinder.I Thefresh 1 r gas and recycle gas are only combined afterthe ,fresh gas has left the cylinder chamber. y The lastdescribed form of the said invention presupposes that the fresh gas, when it is introduced VVinto r. the cylinder chamber within the reactor, has` previously been brought to the same pressure as that which obtains in theotheryparts of the reactor, namely, to the work-" ing pressure of therening process in the reactor'.` Experienee onlthe part ofthe applicants in adapting 'and' perfecting `said process with -coke oventgas as the fresh 1 One-diagrammaticarrangement-according,to the inven- -tionjiisshown in the ,fii'gure of-.the drawing'in--which hoLw- -everffon'ly the: reactor` proper, t i.e. the `chamber sind which is carried-out jthe1 conversion of the initial crude-benzene with'` the rhydrogen-containing` gas andrwith hydrogenation :fof :the impurities, @is shown `in section, `The Lreactorrliis advantageously rconstructed-gin-` the form of a vertical "cypli'ndricjal vessel, f which ris ifilled `with `a Lknown--suitable a catalyst -massf21for-l1ydrogenationi of the-t impurities; and

.zcycler-hydro'genf4 gas charged -with benzene .fv'apors'to be npuritie dat-isi conductedf into the` reactor- 1'- `by-` way;` of-pipes w:i4 is and j 5 ..1from"-a" vaporiser`; device @for -tcrudeg' benzene (which.; device ;-;is" ,not :shown-therein) :and :falso az heater device-,connected :theretmg `the said gas leavingthe-'reacfttor ragainjthr'oughathe discharge 'pipe 6. Thee-:required y'hydrogenation-reactions then- ;takeznplace insideth re`ctors thezinitial temperature-,of the mixture Sor tbenzenes va- :pours anduhvdro'gerr introduced` throughwthatpipes being raised` from 30*320 to about 350-360. From the mixture of vapours withdrawn through the pipe 6, there is then obtained by cooling a-condensation of the'refned r benzene, while the gaswhich has not condensed is supplied again through the pipe 4 to the reactor after the said `gashas become charged with fr eshbenzene vapors. Provided-inside the reactor and preferably laxially there` u of `is ajcylinder, the chamber 7 of` which is'v also lled" with a known catalyst'mass forreduction of sulrfurous andtnitrogenous compounds. This chamber 7 is pro'-V fvvided with a gas supply pipe a discharge piper 1.0,l

the nitric oxides.

acentos and nitric oxide as well as hydrogen, is fedvthrough a pipe 11 into the multi-stage compressor 12, in which it is brought to the necessary lower working pressure of 15 atm. Following the early stage of the compressor in which the fresh gas reaches or substantially reaches a pressure of 15 atm. the said gas is withdrawn from the compressor through a pipe 13 and introduced into a de- Yvice 14, in which the initially compressed gas is heated and charged with steam. Thereafter, the gas passes through the pipe 9 into the chamber 7. By absorption of heat from the reactor 1 while the steam laden fresh coke oven gas is at a pressure of 10-15 atm., reduction of the nitric oxides therein also take place in the chamber I by means of a suitably chosen known catalyst 8 for reduction of nitrogen oxides, in addition to the conversion with steam of the carbon monoxide to hydrogen and carbon dioxide, so that the fresh gas no longer contains one of the two resin-forming constituents, namely, The fresh gas treatedV in this manner leaves the chamber 7 through the pipe 10, then passes through a pipe 15, if necessary into an intermediate cooler 16, in which the gas is cooled to a temperature suitable for the following compressor stage. The gas then passes through a pipe 17`into the next-following compressor stage and is then brought to the working pres sure (about 45 atm.) which is required for the pressurerefining proper. Adanger of resin formation inside the compressor or the pipesron the output side no longer exists, since the hydrogen sulphide still present in the gas has no opportunity of forming resins with nitric oxides. The gas compressed to the full working pressure then passes through a pipe 18 and by way of the regulating valve 19 and the pipe VZ0 into the pipe 5, where it is combined with the mixture of benzene vapour and recycle gas. If necessary, they fresh gas at working pressure can also be conducted beforehand through a heat-exchanger or other heating means, jointly with or separate from the recycle gas, in order to reach a temperature which is the same as or substantially the same as the temperature of the mixture of benzene vapour and recycle gas.

In Ythe constructional form illustrated, the fresh gas innside the conduit-like chamber 7 has a direction of flow vopposite toV the recycle gas in'the reactor.

However, if desired for operational reasons, it is also possible for the fresh gas to be introduced at the top of the chamber 7.and for the recyclel gas also to be introduced at the top or even at therbottoim, so thatthe fresh gas and recycle gas ow opposite to one another or in the same direction as one another in both chambers, i.e'. both in the reactor 1'andthechamber7.l p Y Within thescopefof thepresent invention,l Vthe conduit-like'chamber -7 has for its main object to break down the .nitric oxides'cont'ained in the fresh gas.

carbon dioxide', and hydrogen by the known water gas If conversion of carbon monoxideto In addi-,l tion, a conversion of carbon monoxide with steam to cause a conversion to an appreciable degree is not desired for operational reasons or is not desired at all, the fresh gas does not have to be conducted through the device 14. In this case, the fresh gas is conducted through the pipe 14a to by-pass the device 14.

I claim:

l. In a process for purifying crude benzene contaminatedv with nitrogenous and sulfur compounds, which comprises: treating initial benzene material aforesaid in the vaporphase in a hydrogenation catalyst reactor at an elevated pressure of 40-50 atms. and temperature of 310 C.-360 C. with recycled hydrogen in the presence of a catalyst for hydrogenating impurities contained in the vapor being treated; introducing fresh coke oven gas into the stream containing recycle hydrogen and benzene to replace the hydrogen consumed; and effecting indirect heat exchange within the catalytic hydrogen reactor, between the fresh coke oven gas that is to be introduced and the recycle hydrogen and benzene stream in the catalyst in the catalytic hydrogenation reactor, before mixture of the two gases; the improvement comprising flow ing the fresh coke oven gas at a pressure between 10 and 15 atm. through a catalyst for reduction of nitroge nous compounds during the aforesaid indirect heat exchange of the fresh coke oven gas with the stream containing recycle hydrogen and benzene passing through the hydrogenation catalyst at a pressure of 40-50-atms., to reduce the nitrogenous compounds in -fthe fresh coke oven gas, and thereafter bringing the fresh coke oven gas containing the reduced nitrogenous compounds to the higher working pressure of 40-50 atm. of the stream containing recycle hydrogen and benzene and only thereafter combining the fresh coke oven gas with the stream containing recycle hydrogen and benzene to pass them together through the reactor for hydrogenation as aforesaid at 310 C. to 360 C.

2. A process as claimed in claim 1, characterized by the steps of flowing the fresh coke oven gas through a multi-stage compressor phase for the freshlcoke oven gas in which it is rst raised to a pressure of not more than 15 atm. aforesaid and removed at said pressure from thc compressor and thereupon saturated with steam for conversion of carbon monoxide of the fresh coke oven gas to carbon dioxide and hydrogen, thereafter passing the fresh coke oven gas to the aforesaid catalyst for reduction of nitrogenous compounds while indirect heat exchange within the hydrogenation reactor at said pressure of not more than 15 atm., for effecting said reduction of nitrogenous compounds and completion of the conversion of the carbon monoxide by the steamA to carbon monoxide` and hydrogen, returning the fresh colse oven gas from the catalyst for reduction of nitrogenouscompounds to a higher compressor stage to raise its pressure up to 40-50 atm. forrreaction in the hydrogenation catalyst reactor,

and thereupon combining the fresh coke oven gas with the stream containing recycle hydrogen and benzene.

References Cited in the file of this patent UNITED STATES PATENTS sehmaienbaci; e Mar; 18,1958 

1. IN A PROCESS FOR PURIFYING CRUDE BENZENE CONTAMINATED WITH NITROGENOUS AND SULFUR COMPOUNDS, WHICH COMPRISES: TREATING INITIAL BENZENE MATERIAL AFORESAID IN THE VAPOR PHASE IN A HYDROGENATION CATALYST REACTOR AT AN ELEVATED PRESSURE OF 40-50 ATMS. AND TEMPERATURE OF 310*C.-360*C. WITH RECYCLED HYDROGEN IN THE PRESENCE OF A CATALYST FOR HYDROGENATING IMPURITIES CONTAINED IN THE VAPOR BEING TREATED, INTRODUCING FRESH COKE OVEN GAS INTO THE STREAM CONTAINING RECYCLE HYDROGEN AND BENZENE TO REPLACE THE HYDROGEN CONSUMED, AND EFFECTING INDIRECT HEAT EXCHANGE WITHIN THE CATALYTIC HYDROGEN REACTOR, BETWEEN THE FRESH COKE OVEN GAS THAT IS TO BE INTRODUCED AND THE RECYCLE HYDROGEN AND BENZENE STREAM IN THE CATALYST IN THE CATALYTIC HYDROGENATION REACTOR, BEFORE MIXTURE OF THE TWO GASES, THE IMPROVEMENT COMPRISING FLOWING THE FRESH COKE OVEN GAS AT A PRESSURE BETWEEN 10 AND 15 ATM. THROUGH A CATALYST FOR REDUCTION OF NITROGENOUS COMPOUNDS DURING THE AFORESAID INDIRECT HEAT EXCHANGE OF THE FRESH COKE OVEN GAS WITH THE STREAM CONTAINING RECYCLE HYDROGEN AND BENZENE PASSING THROUGH THE HYDROGENATION CATALYST AT A PRESSURE OF 40-50 ATMS., TO REDUCE THE NITROGENOUS COMPOUNDS IN THE FRESH COKE OVEN GAS, AND THEREAFTER BRINGING THE FRESH COKE OVEN GAS CONTAINING THE REDUCED NITROGENOUS COMPOUNDS TO THE HIGHER WORKING PRESSURE OF 40-50 ATM. OF THE STREAM CONTAINING RECYCLE HYDROGEN AND BENZENE AND ONLY THEREAFTER COMBINING THE FRESH COKE OVEN GAS WITH THE STREAM CONTAINING RECYCLE HYDROGEN AND BENZENE TO PASS THEM TOGETHER THROUGH THE REACTOR FOR HYDROGENATION AS AFORESAID AT 310*C. TO 360*C. 